Adhesive resin and adhesive resin compostion for liquid crystalline polymer

ABSTRACT

An adhesive resin for a liquid crystal polymer, comprising a modified polyolefin (D) prepared by graft polymerizing at least one epoxy group-containing ethylenically unsaturated monomer (B) to a polyolefin (A) obtained by polymerizing one or more olefins selected from ethylene and α-olefin having from 3 to 20 carbon atoms, in an amount in the range of from 0.01 to 50% by weight, with the proviso that the modified polyolefin is 100% by weight. The modified polyolefin (D) can be combined with a thermoplastic resin (E) to form an adhesive resin composition.

TECHNICAL FIELD

The present invention relates to an adhesive resin and an adhesive resincomposition used for a liquid crystal polymer.

BACKGROUND ART

In general, polyolefins are characterized by excellent properties inmoldability, thermal resistance, mechanical characteristics, hygienicadaptability, and steam permeation resistance, and with excellentappearance as molded articles. Therefore, they are widely used inextrusion molded articles, blow molded articles, injection moldedarticles, etc.

However, since the polyolefins are so-called non-polar resins withoutpolar groups in the molecule, they are poor in the affinity with variouspolar materials including metals, and have difficulties in laminatingand using these materials.

Thus, improvement of the affinity with polar materials by graftpolymerization of maleic anhydride to the polylolefins has widely beenused, but the improvement for some adherends is sometimes inadequate,hence a modified polyolefin having higher adhesive force to polarmaterials is desired.

On the other hand, liquid crystal (hereafter referred to as LC) polymersincluding all the aromatic polyesters have excellent chemical resistanceand gas barrier properties, and application to packaging materials forvessels, gasoline tanks of automobiles, etc. has been expected. However,the LC polymer in general has properties of high tendency fororientation in the direction of flow at melting, and hence has highstrength in the molding direction but low strength in the directionperpendicular to molding. Also, because the LC polymers are expensive,it is necessary to use them by laminating with polymers such as thepolyolefins.

Adhesiveness between the LC polymers and the polyolefins in conventionalthermal fusion is poor, and certain adhesive resins are necessary tolaminate them.

Various investigations have so far been performed on the adhesive resinsfor the LC polymers and the polyolefins. These adhesive resins aremainly copolymers manufactured by radical copolymerization of ethyleneand a polar monomer such as (meth)acrylic acid under high pressure.Since many long-chain branches are formed in a polymerization reaction,copolymers with high crystallinity are difficult to be manufactured;hence there were cases in which the adhesive strength is extremelydecreased when the copolymers were applied to usage in direct contactwith a solvent such as gasoline or to usage for fatty food materials.

DISCLOSURE OF INVENTION

The present inventors, in consideration of these conventionaltechnologies, have conducted extensive investigations and as a resultfound that a polyolefin wherein specific ethylenically unsaturatedmonomers are graft polymerized has excellent adhesiveness to the LCpolymer and excellent solvent resistance. Based on these findings thepresent invention has been completed.

An object of the present invention is to provide an adhesive resin andan adhesive resin composition that have excellent adhesiveness to the LCpolymer and excellent solvent resistance.

The adhesive resin for the LC polymer according to the present inventionis characterized by comprising:

-   -   a modified polyolefin (D) prepared by graft polymerizing at        least one epoxy group-containing ethylenically unsaturated        monomer (B) to a polyolefin (A) obtained by polymerizing one or        more olefins selected from ethylene and α-olefin having from 3        to 20 carbon atoms, in an amount in the range of from 0.01 to        50% by weight, with the proviso that the modified polyolefin is        100% by weight.

Examples of the modified polyolefin (D) include a modified polyolefin(D-1) and a modified polyolefin (D-2) to be described later. Themodified polyolefin (D-1) is preferably a modified polyolefin (d-1) tobe described later.

Also, the adhesive resin composition for the LC polymer according to thepresent invention is characterized by comprising a modified polyolefin(D) prepared by graft polymerizing at least one an epoxygroup-containing ethylenically unsaturated monomer (B) to a polyolefin(A) obtained by polymerizing one or more kinds of olefins selected fromethylene and α-olefin having from 3 to 20 carbon atoms, in an amount inthe range of from 0.01 to 50% by weight, with the proviso that themodified polyolefin is 100% by weight; and a thermoplastic resin (E).

BEST MODE FOR CARRAYING OUT THE INVENTION

Next, the adhesive resin and the composition for the LC polymercomprising the same according to the present invention will bespecifically described.

(Polyolefin (A))

The polyolefin (A) to be used in the present invention is obtained bypolymerizing at least one olefin selected from ethylene and α-olefinhaving from 3 to 20 carbon atoms.

Specific examples include α-olefin having from 3 to 20 carbon atoms,such as propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene,1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene,4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, in additionto ethylene. Homopolymers or copolymers thereof can be used alone or incombination with several kinds.

Among them, the polyolefin (A) containing polymers or copolymersobtained from one or more kinds of olefins selected from ethylene,propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene ispreferable.

Among them, the polyolefin (A) containing an ethylene homopolymer (A-1)or a copolymer (A-2) of ethylene and at least one olefin selected fromα-olefin having from 3 to 20 carbon atoms is more preferable. Herein, asfor α-olefins to be copolymerized with ethylene, propylene, 1-butene,4-methyl-1-pentene, 1-hexene and 1-octene are particularly preferable.

In the case where an ethylene-based copolymer is used as the polyolefin(A), the content of ethylene is usually 83 mole % or more, preferably 95mole % or more, and more preferably 97 mole % or more.

The density of the polyolefin (A) used in the present invention isusually 0.895 g/cc or more, preferably 0.900 g/cc or more, morepreferably 0.905 g/cc or more, and most preferably 0.910 g/cc or more,in viewing of obtaining the modified polyolefin having an excellentbalance between adhesiveness to the LC polymer and solvent resistance.

The melt flow rate (MFR; ASTM D 1238, at 190° C. under a load of 2.16kg) of the polyolefin (A) is usually in the range of from 0.01 to 500g/10 minutes, preferably from 0.05 to 200 g/10 minutes, and morepreferably from 0.1 to 100 g/10 minutes.

The crystallinity of the polyolefin (A) is usually 10% or more,preferably 25% or more, and more preferably 35% or more.

Also, the weight average molecular weight (Mw) measured by gelpermeation chromatography (GPC) is usually in the range of from 5,000 to1,000,000, preferably from 8,000 to 500,000, and more preferably from10,000 to 200,000.

The molecular weight distribution (Mw/Mn) is usually 0.6 or less,preferably 5.5 or less, and more preferably 5.0 or less. In addition, Mnrefers to the number average molecular weight.

Manufacturing of the above polyolefin can be carried out by any one ofknown conventional methods, for example, by polymerization usingtitanium-based catalysts, vanadium-based catalysts, metallocenecatalysts, etc.

(Epoxy Group-Containing Ethylenically Unsaturated Monomer (B))

The epoxy group-containing ethylenically unsaturated monomer is amonomer containing at least one of a polymerizable unsaturated bond andat least one of an epoxy group in the molecule. Examples of the epoxygroup-containing ethylenically unsaturated compound include glycidylacrylate; glycidyl (meth)acrylate; mono- and alkylglycidyl esters(wherein the alkyl group for the monoglycidyl ester has 1 to 12 carbonatoms) of dicarboxylic acids such as, mono- and diglycidyl esters ofmaleic acid, mono- and diglycidyl esters of fumaric acid, mono- anddiglycidyl esters of crotonic acid, mono- and diglycidyl esters oftetrahydrophthalic acid, mono- and glycidyl esters of itaconic acid,mono- and diglycidyl esters of butene tricarboxylic acid, mono- anddiglycidyl esters of citraconic acid, monoglycidyl and diglycidyl estersof endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (nadic acidTM), mono- and diglycidyl esters ofendo-cis-bicyclo[2.2.1]hept-5-ene-2-methyl-2,3-dicarboxylic acid (methylnadic acid TM) and mono- and glycidyl esters of allyl succinic acid;alkyl glycidyl esters of p-styrene carboxylic acid; allyl glycidylether; 2-methylallyl glycidyl ether; styrene-p-glycidyl ether;3,4-epoxy-1-butene; 3,4-epoxy-3-methyl-1-butene; 3,4-epoxy-1-pentene;3,4-epoxy-3-methyl-1-pentene; and 5,6-epoxy-1-hexene.

Among these compounds, it is preferable to use glycidyl acrylate,glycidyl (meth)acrylate, mono- and diglycidyl esters of maleic acid.

(Alicyclic Epoxy Group-Containing Ethylenically Unsaturated Monomer)

In addition, in addition to these, examples of the epoxygroup-containing ethylenically unsaturated monomer (B) used in thepresent invention include preferably the alicyclic epoxygroup-containing ethylenically unsaturated monomer represented by thefollowing formulae (1) to (5):

-   -   (wherein R₁ is a hydrogen atom or a methyl group, R₂ is a single        bond or a bivalent hydrocarbon group having from 1 to 20 carbon        atoms and optionally containing hetero atoms, R₃ is a hydrogen        atom or a hydrocarbon group having from 1 to 20 carbon atoms and        optionally containing hetero atoms, and n is an integer between        0 and 2, with the proviso that R₃ may be all the same or        different from each other.)

Examples of the bivalent hydrocarbon group having from 1 to 20 carbonatoms and optionally containing hetero atoms, of R₂, include an alkylenegroup such as methylene, ethylene, propylene, and butylene, a(poly)alkylene oxide such as ethylene oxide and polyethylene oxide, andan arylene group such as phenylene group.

Examples of the hydrocarbon group having from 1 to 20 carbon atoms andoptionally containing hetero atoms, of R₃, include an alkyl group suchas methyl, ethyl, propyl, and butyl, a hydroxyl group, and an alkoxygroup such as methoxy and ethoxy.

Specific examples of these compounds include compounds represented bythe following structural formulae:

(Aromatic Vinyl Monomer (C))

In the present invention, it is preferable to use the aromatic vinylmonomer (C) simultaneously with the epoxy group-containing ethylenicallyunsaturated monomer.

Examples of the aromatic vinyl monomer (C) include a compoundrepresented by the following formula [I]:

In the above formula [I], R⁶ and R⁷ may be the same or different eachother, and is a hydrogen atom or an alkyl group having from 1 to 3carbon atoms, and specific examples thereof include a methyl group, anethyl group, a propyl group and an isopropyl group. Also, R⁸ is ahydrocarbon group having from 1 to 3 carbon atoms or a halogen atom, andspecific examples thereof include a methyl group, an ethyl group, apropyl group, an isopropyl group, a chlorine atom, a bromine atom or aniodine atom. Further, n is an integer usually between 0 and 5, andpreferably of 1 to 5. In addition, [Φ]in the formula [I] is an aromaticring optionally containing hetero atoms. In addition, R⁷ may be all thesame or different from each other, and R⁸ may be all the same ordifferent from each other.

Specific examples of the aromatic vinyl monomer include styrene,α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene,p-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 4-vinyl pyridine,2-vinyl pyridine, 5-ethyl-2-vinyl pyridine, 2-methyl-5-vinyl pyridine,2-isopropenyl pyridine, 2-vinyl quinoline, 3-vinyl isoquinoline, N-vinylcarbazole, and N-vinyl pyrrolidone.

(Ethylenically Unsaturated Monomer Other Than (B) and (C))

In the present invention, the ethylenically unsaturated monomer otherthan the epoxy group-containing ethylenically unsaturated monomer (B)and the aromatic vinyl monomer (C) is optionally used, provided thatsuch monomers are within the spirit or scope of the present invention.

Examples of the ethylenically unsaturated monomers that may be used inthe present invention include hydroxyl group-containing ethylenicallyunsaturated compounds, amino group-containing ethylenically unsaturatedcompounds, unsaturated carboxylic acids and derivatives thereof, vinylester compounds, vinyl chlorides, and oxazoline group-containingunsaturated monomers.

Specific examples of the hydroxyl group-containing ethylenicallyunsaturated compounds include (meth)acrylic acid esters, such as,hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,3-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerinmono(meth)acrylate, pentaerythritol mono(meth)acrylate,trimethylolpropane mono(meth)acrylate, tetramethylolethanemono(meth)acrylate, butanediol mono(meth)acrylate, polyethyleneglycolmono (meth) acrylate, and 2(6-hydroxyhexanoyloxy) ethylacrylate, as wellas 10-undecen-1-ol, 1-octen-3-ol, 2-methanolnorbornene, hydroxystyrene,hydroxyethyl vinyl ether, hydroxybutyl vinyl ether,N-methylolacrylamide, 2-(meth)acryloyloxyethyl acid phosphate, glycerinmonoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol andglycerin monoalcohol.

The amino group-containing ethylenically unsaturated compound is acompound containing ethylenic double bond(s) and amino group(s). Forsuch compounds, there can be exemplified a vinyl monomer having at leastone amino group or a substituted amino group represented by thefollowing formula:C(R4)₂=CR4-COO—(CH₂)mN(R5)₂  [II]

In the formula [II], each R4 is independently a hydrogen atom, a methylgroup or an ethyl group, each R5 is independently a hydrogen atom, analkyl group having from 1 to 12 carbon atoms, preferably 1 to 8 carbonatoms or a cycloalkyl group having from 6 to 12 carbon atoms, preferably6 to 8 carbon atoms. In addition, the alkyl group or the cycloalkylgroup may further have a substituent. Further, m is an integer between 1and 5, preferably 1 to 3.

Specific examples of the amino group-containing ethylenicallyunsaturated compound include alkyl ester derivatives of acrylic acid ormethacrylic acid, such as aminoethyl (meth)acrylate, propylaminoethyl(meth)acrylate, dimethylaminoethyl methacrylate, aminopropyl(meth)acrylate, phenylaminoethyl methacrylate, and cyclohexylaminoethylmethacrylate; vinylamine derivatives such as N-vinyldiethylamine andN-acetylvinylamine; allylamine derivatives such as allylamine,methacrylamine, N-methylacrylamine, N,N-dimethylacrylamide, andN,N-dimethylaminopropylacrylamide; acrylamide derivatives such asacrylamide and N-methylacrylamide; aminostyrenes such as p-aminostyrene;imide 6-aminohexylsuccinate and imide 2-aminoethylsuccinate.

As the unsaturated carboxylic acid, there may be exemplified unsaturatedcarboxylic acids, such as, acrylic acid, methacrylic acid, maleic acid,fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid,crotonic acid, isocrotonic acid, norbornene dicarboxylic acid,bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid, or their anhydrides ortheir derivatives (for example, acid halides, amides, imides, esters,etc.).

Specific examples include malenyl chloride, malenyl imide, maleicanhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalicanhydride, bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid anhydride,dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate,dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate,dimethyl bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylate, hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate,aminoethyl methacrylate and aminopropyl methacrylate. Among them,(meth)acrylic acid, maleic anhydrid, hydroxyethyl (meth)acrylate,glycidyl methacrylate and aminopropyl methacrylate are preferred.

Examples of the vinyl ester compound include vinyl acetate, vinylpropionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinylcaproate, vinyl versatate, vinyl laurate, vinyl stearate, vinylbenzoate, vinyl p-t-butylbenzoate, vinyl salicylate, and vinylcyclohexanecarboxylate.

Specific examples of the oxazoline group-containing unsaturated monomerinclude 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline,4,4-dimethyl-2-vinyl-2-oxazoline,4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine,4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine,2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline,ricinoloxazoline acrylate, ricinoloxazoline methacrylate, andricinoloxazoline maleate. Among them, ricinoloxazoline acrylate,ricinoloxazoline methacrylate and ricinoloxazoline maleate arepreferred.

Examples of the modified polyolefin (D) suitable as an adhesive resinfor the LC polymer of the present invention include the modifiedpolyolefin (D-1).

Modified Polyolefin (D-1)

The modified polyolefin (D-1) formed by graft polymerizing 0.01 to 20%by weight of the epoxy group-containing ethylenically unsaturatedmonomer (B) to the polyolefin (A) wherein the polyolefin (A) is anethylene homopolymer (A-1) or a copolymer (A-2) of ethylene and at leastone α-olefin selected from α-olefin having from 3 to 20 carbon atoms,the ethylene homopolymer (A-1) or the copolymer (A-2) has a density of0.895 g/cc or more, a melt flow rate (190° C. and a load of 2.16 kg) iswithin the range of from 0.01 to 500 g/10 minutes (with the provisothat, in the modified polyolefin (D-1), the epoxy group-containingethylenically unsaturated monomer (B) is the epoxy group-containingethylenically unsaturated monomer excluding the alicyclic epoxygroup-containing ethylenically unsaturated monomers represented by theabove formulae (1) to (5)).

As the modified polyolefin (D-1), the following modified polyolefin(d-1) is more preferred.

Modified Polyolefin (d-1)

The modified polyolefin formed by graft polymerizing 0.01 to 20% byweight of the epoxy group-containing ethylenically unsaturated monomer(B) and 0.01 to 20% by weight of the aromatic vinyl monomer (C) to thepolyolefin (A) wherein the polyolefin (A) is an ethylene homopolymer(A-1) or a copolymer (A-2) of ethylene and at least one α-olefinselected from α-olefin having from 3 to 20 carbon atoms, the ethylenehomopolymer (A-1) or the copolymer (A-2) has a density of 0.895 g/cc ormore and a melt flow rate (190° C. and a load of 2.16 kg) is within therange of from 0.01 to 500 g/10 minutes.

The modified polyolefin (d-1) of the present invention can bemanufactured by reacting the polyolefin (A) with the epoxygroup-containing ethylenically unsaturated monomer (B), and the aromaticvinyl monomer (C), and, if necessary, the ethylenically unsaturatedmonomer other than (B) and (C) under heating in the presence or absenceof a radical initiator.

The reaction efficiency of this graft polymerization is increased whenperformed in the presence of the radical initiator, hence it ispreferable to carry out graft reaction using the radical initiator inmanufacturing the modified polyolefin (d-1) of the present invention.

Examples of the radical initiator used herein include an organicperoxide or an azo compound.

Specific examples of the organic peroxide include dicumyl peroxide,di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane,2,5-dimethyl-2,5-bis(t-butylperoxy) hexyne-3, 1, 3-bis(t-butylperoxyisopropyl) benzene, 1,1-bis(t-butylperoxy)valerate,benzoyl peroxide, t-butylperoxy benzoate, acetyl peroxide, isobutyrylperoxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide andm-toluyl peroxide. In addition, examples of the azo compound includeazoisobutyronitrile and dimethylazoisobutyronitrile.

The radical initiator is used in general in an amount of 0.001 to 10parts by weight, preferably 0.05 to 5 parts by weight per 100 parts byweight of the polyolefin (A). The radical initiator can be employed assuch by mixing with the polyolefin (A), or can be also used bydissolving it in a small amount of an organic solvent.

As the organic solvent to be employed here, every organic solventcapable of dissolving the radical initiator can be used without anyrestriction. Examples of the organic solvent include an aromatichydrocarbon solvent such as benzene, toluene and xylene; an aliphatichydrocarbon solvent such as pentane, hexane, heptane, octane, nonane anddecane; an alicyclic hydrocarbon solvent such as cyclohexane,methylcyclohexane and decahydronaphthalene; a chlorinated hydrocarbonsuch as chlorobenzene, dichlorobenzene, trichlorobenzene, methylenechloride, chloroform, carbon tetrachloride and tetrachloroethylene; analcohol solvent such as methanol, ethanol, n-propinol, iso-propanol,n-butanol, sec-butanol and tert-butanol; a ketone solvent such asacetone, methyl ethyl ketone and methyl isobutyl ketone; an estersolvent such as ethyl acetate and dimethyl phthalate; and an ethersolvent such as dimethyl ether, diethyl ether, di-n-amyl ether,tetrahydrofuran and dioxyanisole.

In addition, in the present invention, on graft-modifying the polyolefin(A), a reducing substance may also be used. The reducing substance has afunction of increasing the grafted amount in the resulting modifiedpolyolefin (d-1).

Examples of the reducing substance include iron (II) ion, chromium ion,cobalt ion, nickel ion, palladium ion, sulfite, hydroxyamine, hydrazine,as well as compounds having groups such as —SH, —SO₃H, —NHNH₂, and—COCH(OH)—.

Specific examples of these reducing substances include ferrous chloride,potassium bichromate, cobalt chloride, cobalt naphthenate, palladiumchloride, ethanolamine, diethanolamine, N,N-dimethylaniline, hydrazine,ethyl mercaptan, benzenesulfonic acid, and p-toluenesulfonic acid.

The reducing substance mentioned above is used usually in an amount of0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight per 100parts by weight of the polyolefin (A).

The graft polymerization stated above may be performed under any of thefollowing conditions in that at least part of the polyolefin (A) is in asolid state, molten state, or at least partly dissolved in an organicsolvent.

In the case where the graft polymerization is performed under theconditions where at least part of the thermoplastic polymer is dissolvedin an organic solvent, it is performed usually at 50 to 200° C.,preferably at 60 to 190° C., and more preferably at 70 to 180° C.

The organic solvent used in the graft polymerization is any of thosecapable of dissolving the thermoplastic polymer, and is not particularlylimited. Examples of the organic solvent suitable for use with theethylenic polymer (A) include aromatic hydrocarbon solvents such asbenzene, toluene and xylene, and aliphatic hydrocarbon solvents such aspentane, hexane, and heptane.

Also, the epoxy group-containing ethylenically unsaturated monomer (B)and the aromatic vinyl monomer (C) are added by the following methods:

(1) (B) and (C) are added all at once before initiation of reaction, (2)either of (B) and (C) is added before initiation of reaction,temperature is increased and the other monomer is added, and (3) afterboth (B) and (C) are warmed, they are added by dropping for apredetermined period. Among them, use of method (3), wherein after both(B) and (C) are warmed, they are added by dropping for the predeterminedperiod is preferable.

In addition, in this case, (B) and (C) may be dropped using separateinlet tubes or may be added (dropped) by mixing them. The latter methodis preferable.

In the case where the radical polymerization initiator is used, it maybe added all at once before initiation of reaction, or may be dropped ina predetermined duration after heating. The latter method, wherein theinitiator is dropped in a predetermined duration after heating, ispreferable. In this case, the radical polymerization initiator isdropped preferably through a separate inlet tube independently from (B)and (C) inlet tubes.

Also, in the case where the graft polymerization is carried out underthe conditions in which the polyolefin (A) is in a molten state, thereaction is carried out usually at temperatures higher than the meltingpoint of the polyolefin (A). That is, graft polymerization reaction iscarried out at temperatures higher than the melting point of thepolyolefin (A), specifically, usually at 80 to 300° C., and preferablyat 80 to 250° C.

In the case where an extruder is used in graft polymerization, examplesof the method include a method wherein:

(1) the polyolefin (A), the epoxy group-containing ethylenicallyunsaturated monomer (B) and the aromatic vinyl monomer (C), andoptionally the radical initiator are premixed and the resulting mixtureis fed through a hopper; or (2) the polyolefin (A) and the aromaticvinyl monomer (C), and optionally the radical initiator are fed througha hopper, and the epoxy group-containing ethylenically unsaturatedmonomer (B) optionally dissolved in the solvent is fed through an inletprovided at an arbitrary place between a hopper part and the tip of theextruder.

The grafted amount of the epoxy group-containing ethylenicallyunsaturated monomer in the modified polyolefin (d-1) prepared as aboveis usually in the range of from 0.01 to 20% by weight, preferably from0.02 to 15% by weight, and more preferably from 0.03 to 10% by weight.

In addition, the grafted amount of the aromatic vinyl monomer containedin the modified polyolefin (d-1) is usually in the range of from 0.01 to20% by weight, preferably from 0.02 to 15% by weight, and morepreferably from 0.03 to 10% by weight.

The mole ratio between the epoxy group-containing ethylenicallyunsaturated monomer (B) and the aromatic vinyl monomer (C) that aregraft polymerized in the modified polyolefin (d-1) of the presentinvention is usually from 10:90 to 95:5, preferably from 20:80 to 90:10,more preferably from 25:75 to 85:15, and most preferably from 30:70 to80:20.

In the case where the epoxy group-containing ethylenically unsaturatedmonomer (B) and the aromatic vinyl monomer (C) are graft polymerizedwith these mole ratios, the modified polyolefin (d-1) thus obtained hasexcellent adhesiveness to the LC polymer and excellent solventresistance.

Examples of the modified polyolefin (D) suitable as the adhesive resinfor the LC polymer of the present invention include the modifiedpolyolefin (D-2) described below:

Modified Polyolefin (D-2)

The modified polyolefin prepared by graft polymerizing at least onealicyclic epoxy group-containing ethylenically unsaturated monomerrepresented by the above formulae (1) to (5) to a polyolefin (A)obtained by polymerizing one or more olefins selected from ethylene andα-olefin having from 3 to 20 carbon atoms, in an amount in the range offrom 0.01 to 50% by weight, with the proviso that the modifiedpolyolefin is 100% by weight.

The modified polyolefin (D-2) is preferably prepared by graftpolymerizing at least one alicyclic epoxy group-containing ethylenicallyunsaturated monomer (B) represented by the above formulae (1) to (5) inthe range of from 0.01 to 50% by weight, and the other ethylenicallyunsaturated monomer in the range of from 0.01 to 50% by weight to apolyolefin (A) obtained by polymerizing one or more olefins selectedfrom ethylene and α-olefin having from 3 to 20 carbon atoms, with theproviso that the modified polyolefin is 100% by weight and the totalgrafted amount of (B) and the other ethylenically unsaturated monomer isin the range of from 0.02 to 60% by weight.

In this case, the polyolefin (A) is preferably the ethylene homopolymer(A-1) or the ethylene copolymer (A-2), and the density of the polyolefin(A) is preferably 0.895 g/cc. In addition, the other ethylenicallyunsaturated monomer is preferably the aromatic vinyl monomer (C).

Graft Polymerization

The modified polyolefin (D-2) of the present invention can be obtainedby graft polymerization of the polyolefin (A) with at least onealicyclic epoxy group-containing ethylenically unsaturated monomer (B)represented by the aforementioned formulae (1) to (5) and optionally theother ethylenically unsaturated monomer, by heating in the presence orabsence of the radical initiator.

Graft polymerization is preferably carried out in the presence of theradical initiator so that graft polymerization reaction efficiency ishigher. Examples of the radical initiator used herewith include theorganic peroxide or the azo compound.

Specific examples of the organic peroxide and the azo compound aresimilar to those listed in the aforementioned modified polyolefin (d-1).

The radical initiator is preferably used in general in the range of from0.001 to 10 parts by weight per 100 parts by weight of the polyolefin.

The radical initiator can be employed as such by mixing with thepolyolefin (A) and the alicyclic epoxy group-containing ethylenicallyunsaturated monomer, or can be also used by dissolving it in a smallamount of an organic solvent. As the organic solvent to be employedhere, every organic solvent capable of dissolving the radical initiatorcan be used without any particular restriction.

Examples of the organic solvent are similar to those listed in theaforementioned modified polyolefin (d-1).

In addition, in the present invention, on graft-modifying thepolyolefin, a reducing substance may also be used. The reducingsubstance has a function of increasing the grafted amount in theresulting modified polyolefin.

Examples of the reducing substance are similar to those listed in theaforementioned modified polyolefin (d-1).

The above reducing substances are used usually in the range of from0.001 to 5 parts by weight, preferably in the range of from 0.1 to 3parts by weight per 100 parts by weight of polyolefin (A).

The graft polymerization stated above may be performed under any of thefollowing conditions in that at least part of the polyolefin (A) is in asolid state, molten state, or at least partly dissolved in an organicsolvent.

In the case where the graft polymerization is performed under theconditions where at least part of the polyolefin (A) is dissolved in anorganic solvent, it is performed usually at 50 to 200° C., preferably at60 to 190° C., and more preferably at 70 to 180° C.

The organic solvent used in the graft polymerization is any of thosecapable of dissolving the polyolefin (A), and is not particularlylimited. Examples of the organic solvent include aromatic hydrocarbonsolvents such as benzene, toluene and xylene, and aliphatic hydrocarbonsolvents such as pentane, hexane, and heptane.

Also, in the case where the graft polymerization is carried out underthe condition where the polyolefin (A) is in a molten state, thereaction temperature is usually higher than the melting point of thepolyolefin. Specifically, the reaction temperature is usually at 80 to300° C., and preferably at 80 to 250° C.

In the case where an extruder is used in the graft polymerization,examples of the method include a method wherein:

(1) the polyolefin, the alicyclic epoxy group-containing ethylenicallyunsaturated monomer (including optionally the other ethylenicallyunsaturated monomer) and optionally the radical initiator are premixedand the resulting mixture is fed to the extruder through a hopper, and(2) the polyolefin and optionally the radical initiator are fed to theextruder through a hopper, and the alicyclic epoxy group-containingethylenically unsaturated monomer optionally dissolved in the solvent isfed through an inlet provided at an arbitrary place between hopper partand the tip of the extruder.

In addition, in the case where both the alicyclic epoxy group-containingethylenically unsaturated monomer (B) and the other ethylenicallyunsaturated monomer are graft polymerized, each monomer may be mixed andthen added, each monomer may be added through separate inlet tubes, orone monomer may be added after the other monomer is added. Among them,the method wherein the alicyclic epoxy group-containing ethylenicallyunsaturated monomer (B) and the other ethylenically unsaturated monomerare mixed and then added, or the method where each monomer is added tothe reaction system through the separate inlet tubes is preferable asthe method gives high grafting efficiency, and yields the modifiedpolyolefin (D-2) with excellent adhesiveness performance.

The grafted amount of the grafted groups derived from the alicyclicepoxy group-containing ethylenically unsaturated monomer in the thusprepared modified polyolefin (D-2) is usually in the range of from 0.01to 50% by weight, preferably from 0.02 to 30% by weight, more preferablyfrom 0.03 to 10% by weight, and most preferably from 0.03 to 5% byweight, with respect to the modified polyolefin as 100% by weight.

In the present invention, in the case where the other ethylenicallyunsaturated monomer is graft polymerized with the alicyclic epoxygroup-containing ethylenically unsaturated monomer (B), the graftedamount of the other ethylenically unsaturated monomer is usually in therange of from 0.01 to 50% by weight, preferably from 0.02 to 30% byweight, more preferably from 0.03 to 10% by weight, and most preferablyfrom 0.03 to 5% by weight. Note however, in this case the total graftedamount of the alicyclic epoxy group-containing ethylenically unsaturatedmonomer (B) and the other ethylenically unsaturated monomer is usuallyfrom 0.02 to 60% by weight, preferably from 0.03 to 40% by weight, morepreferably from 0.04 to 20% by weight, and most preferably from 0.06 to10% by weight.

Also, the ratio of the grafted amount of the alicyclic epoxygroup-containing ethylenically unsaturated monomer (B) and that of theother ethylenically unsaturated monomer is usually from 99.5:0.5 to1.0:99.0, preferably from 90:10 to 5:95, and more preferably from 80:20to 10:90.

As stated above, the method of the graft polymerization is explainedwith the modified polyolefins (d-1) and (D-2) as examples. The modifiedpolyolefin (D) other than those described above can be manufactured bythe graft polymerization according to the condition described above or acondition with appropriate changes.

(Adhesive Resin and Adhesive Resin Composition)

The adhesive resin for the LC polymer of the present invention ischaracterized by comprising the modified polyolefin described above.

Also, the adhesive resin composition for the LC polymer of the presentinvention may be formed from two or more kinds of polymers selected fromthe modified polyolefin (D) described above, or from the modifiedpolyolefin (D) described above and the thermoplastic resin (E) otherthan said polymers.

Particularly, the adhesive resin composition preferably comprises 1 to90% by weight of the modified polyolefin (D), based on the total of themodified polyolefin (D) and the thermoplastic resin (E) as 100% byweight.

In the present invention, one kind of the thermoplastic resin (E)selected from the listed below is preferably used: polyolefin,polyamide, polyester, polyacetal, polystyrene,acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate,polycarbonate, polyphenylene oxide, polyvinyl chloride, polyvinylidenechloride, polyvinyl acetate and ethylene-(meth)acrylate ester copolymer,diene-based polymer.

Examples of the polyolefin include olefin homopolymers such aspolyethylene, polypropylene, poly-1-butene, polymethylpentene, andpolymethylbutene; and olefin copolymers such as ethylene-α-olefin randomcopolymer, ethylene-propylene-diene ternary copolymer,propylene-ethylene random copolymer, propylene-α-olefin randomcopolymer, propylene-ethylene-α-olefin ternary copolymer. Among them,polyethylene, polyproylene, ethylene-α-olefin random copolymer,ethylene-propylene-diene ternary copolymer, propylene-ethylene randomcopolymer, and propylene-α-olefin random copolymer are preferably used.In addition, in the case where the polyolefin is obtained from an olefinhaving three or more carbon atoms, it may be an isotactic polymer or asyndiotactic polymer.

Also, any of known catalysts such as Ziegler-Natta type catalyst ormetallocene catalyst catalysts may be used for manufacture of thepolyolefin.

Examples of the polyamide include aliphatic polyamides such as nylon-6,nylon-66, nylon-10, nylon-12 and nylon-46; and aromatic polyamidesmanufactured from aromatic dicarboxylic acids and aliphatic diamines, ofwhich nylon-6 is preferable.

Examples of the polyester include aromatic polyesters such aspolyethylene terephthalate, polyethylene naphthalate, and polybutyleneterephthalate, polycaprolactone, and polyhydroxybutyrate, of whichpolyethylene terephthalate is preferable.

Examples of the polyacetal include polyformaldehyde (polyoxymethylene),polyacetaldehyde, polypropionaldehyde, and polybutylaldehyde, of whichpolyformaldehyde is particularly preferable.

The polystyrene may be a styrene homopolymer, or a binary copolymerbetween styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene such as acrylonitrile-styrene copolymer.

For ABS, those comprising a structural unit derived from acrylonitrilein the range of from 20 to 35 mole %, a structural unit derived frombutadiene in the range of from 20 to 30 mole % and a structural unitderived from styrene in the range of from 40 to 60 mole % are preferablyused.

For polymethacrylate, polymethyl methacrylate (PMMA) is preferable.

Examples of polycarbonates-include those-obtained frombis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane, or 2,2-bis(4-hydroxyphenyl)butane, ofwhich polycarbonate obtained from 2,2-bis(4-hydroxyphenyl)propane ispreferable.

For the polyphenylene oxide, poly(2,6-dimethyl-1,4-phenylene oxide) ispreferable.

The polyvinyl chloride may be a vinyl chloride homopolymer, or acopolymer with vinylidene chloride, acrylic acid ester, acylonitrile,propylene, etc.

For the polyvinylidene chloride, a copolymer with vinyl chloride,acrylonitrile, (meth)acrylic acid ester, allylester, unsaturated ether,and styrene containing 85% or more of the vinylidene chloride unit isusually used.

The polyvinyl acetate may be a vinyl acetate homopolymer, or a copolymerwith ethylene or vinyl chloride, of which the ethylene-vinyl acetatecopolymer is preferable.

For the ethylene-(meth)acrylic acid ester copolymer, anethylene-methylacrylate copolymer, an ethylene-ethylacrylate copolymer,an ethylene-methylmethacrylate copolymer, or anethylene-ethylmethacrylate copolymer is preferable.

Examples of the diene-based polymer include polybutadiene, polyisoprene,or aromatic hydrocarbon-based block copolymer which is optionallyhydrogenated.

The aromatic hydrocarbon-based block copolymer that is optionallyhydrogenated is an aromatic-vinyl-conjugated diene block copolymercomprising a block polymer unit (X) derived from an aromatic vinyl and ablock polymer unit (Y) derived from a conjugated diene, and ahydrogenated derivative thereof.

The chemical form of the aromatic vinyl-conjugated diene block copolymeris represented by X(YX)_(n) or (XY)n (where n is an integer of one ormore), for example.

Among them, a block copolymer in the form of X(YX)_(n), particularly ofX-Y-X, is preferable, and specifically the styrene-based block copolymerin the form of polystyrene-polybutadiene (or polyisoprene orpolyisoprene-butadiene)-polystyrene is preferable.

In the styrene-based block copolymer, an aromatic vinyl block polymerunit (X) which is a hard segment acts as a crosslinking point for aconjugated diene block polymer unit (Y), thus forming a physicalcrosslinking (domain). The conjugated diene block polymer unit (Y)present among the aromatic vinyl block polymer unit (X) is a softsegment and has rubber elasticity.

Specific examples of the aromatic vinyl compound forming the blockpolymer unit (X) described above include, besides styrene, styrenederivatives such as α-methylstyrene, 3-methylstyrene, p-methylstyrene,4-propylstyrene, 4-dodecylstyrene, 4-cyclohexylstyrene,2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene. Among them, styrene ispreferable.

Also, examples of the conjugated diene forming the block polymer unit(Y) include butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene, andtheir combination. Among them, butadiene or isoprene or a combination ofbutadiene and isoprene is preferable.

In the case where the conjugated diene block polymer unit (Y) is derivedfrom butadiene and isoprene, it contains preferably 40 mole % or more ofan isoprene-derived unit.

In addition, the conjugated diene block polymer unit (Y) comprising sucha butadiene-isoprene copolymer unit may be a random polymer unit, or ablock copolymer unit, or a tapered copolymer unit between butadiene andisoprene.

The aromatic vinyl-conjugated diene block copolymer described abovecomprises 22% by weight or less, preferably 5 to 22% by weight of thearomatic vinyl block polymer unit (X). The amount of the aromatic vinylpolymer unit can be measured by conventional methods such as infraredspectroscopy, NMR spectroscopy, etc.

Also, the melt flow rate (MFR; ASTM D 1238, 200° C. and a load of 2.16kg) of the aromatic vinyl-conjugated diene block copolymer is usually 5g/10 minutes or more, preferably 5 to 100 g/10 minutes.

Various methods for manufacturing the aromatic vinyl-conjugated dieneblock copolymer are available. Examples thereof include:

-   -   (1) a method wherein the aromatic vinyl compound and then the        conjugated diene are consecutively polymerized with an        alkyllithium compound such as n-butyllithium as an initiator,    -   (2) a method wherein the aromatic vinyl compound and then the        conjugated diene are polymerized, and the resultant polymer is        coupled using a coupling agent,    -   (3) a method wherein the conjugated diene and then the aromatic        vinyl compound are consecutively polymerized using a lithium        compound as an initiator, etc.

In addition, the hydrogenated aromatic vinyl-conjugated diene blockcopolymer can be obtained by hydrogenation of the aforementionedaromatic vinyl-conjugated diene block copolymer using known methods. Thehydrogenated aromatic vinyl-conjugated diene block copolymer haveusually a hydrogenation degree of 90% or more.

The hydrogenation degree is based on the total amount of carbon-carbondouble bonds in the conjugated diene block polymer unit (Y) as being100%.

Specific examples of the hydrogenated aromatic vinyl-conjugated dieneblock copolymer include a hydrogenated styrene-isoprene block copolymer(SEP), a hydrogenated styrene-isoprene-styrene block copolymer (SEPS; apolystyrene-polyethylene/propylene-polystyrene block copolymer), and ahydrogenated styrene-butadiene block copolymer (SEBS; apolystyrene-polyethylene/butylene-polystyrene block copolymer). Morespecifically, examples thereof include HYBRAR (trade name, produced byKuraray Co., Ltd.), Kraton (trade name, produced by Shell Chemical Co.,Ltd.), Cariflex TR (trade name, produced by Shell Chemical Co., Ltd.),Solprene (trade name, produced by Phillips Petroleum Co., Ltd.),Europrene SOLT (trade name, produced by Anic S. p. A.), Tufprene (tradename, produced by Asahi Kasei Corporation), Solprene-T (trade name,produced by Japan Elastomer Co., Ltd.), JSR-TR (trade name, produced byJapan Synthetic Rubber Co., Ltd.), Denka STR (trade name, produced byDenki kagaku Kogyo K.K.), Quintack (trade name, produced by ZeonCorporation), Kraton G (trade name, produced by Shell Chemical Co.,Ltd.) and Tuftec (trade name, produced by Asahi Kasei Corporation).

The thermoplastic resin (E) described above may be used alone or incombination with 2 or more kinds.

Among examples of the thermoplastic resin (E), polyolefin, polyester,polyamide, polystyrene, and diene-based polymer are preferably used.

In the case where the polyolefin is used as the thermoplastic resin (E),at least one ethylenic polymer selected from the ethylene homopolymerand at least one ethylenic copolymer comprising ethylene and at leastone α-olefin selected from the α-olefins having from 3 to 20 carbonatoms are used preferably. Among the α-olefins that are copolymerizedwith ethylene, particularly preferable are propylene, 1-butene,4-methyl-1-pentene, 1-hexene and 1-octene.

In the case where the ethylenic copolymer is used as the polyolefin, theamount of ethylene is usually 95 mole % or more, preferably 97 mole % ormore, and more preferably 98 mole % or more.

The density of the ethylenic polymer used in the present invention isusually 0.895 g/cc or more, preferably 0.900 g/cc or more, and morepreferably 0.910 g/cc or more.

A value of MFR of the ethylenic polymer used in the present inventionmeasured at 190° C. is usually in the range of from 0.01 to 500 g/10minutes, preferably from 0.05 to 200 g/10 minutes, and more preferablyfrom 0.1 to 100 g/10 minutes.

The crystallinity of the ethylenic polymer used in the present inventionis usually 25% or more, preferably 30% or more, and more preferably 35%or more.

The weight average molecular weight (Mw) of the ethylenic polymer usedin the present invention measured by gel permeation chromatography (GPC)is usually in the range of from 5,000 to 1,000,000, preferably from8,000 to 500,000, and more preferably from 10,000 to 200,000.

Also, the molecular weight distribution (Mw/Mn) is usually 6.0 or less,preferably 5.5 or less, and more preferably 5.0 or less.

The polyolefin described above can be manufactured by any of knownmethods, for example, by polymerization using a titanium-based catalyst,a vanadium-based catalyst and a metallocene catalyst.

The adhesive resin and the adhesive resin composition of the presentinvention can be used for adhesion between the polyolefin and the LCpolymer, between the LC polymer and the LC polymer, between the LCpolymer and another polar resin.

Examples of the polar resins other than the LC polymer that can beadhered to the adhesive resin composition of the present inventioninclude polyamide, polyester, polyacetal, polystyrene,acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate,polycarbonate, polyphenylene oxide, polyvinyl chloride, andpolyvinylidene chloride.

(Other Additives)

The adhesive resin and the adhesive resin composition used in thepresent invention may contain a crosslinking agent, a filler, acrosslinking promoter, a crosslinking auxiliary agent, a softeningagent, a tackifier, an antioxidant, a foaming agent, a processing aid,an inorganic filler, an organic filler, a crystal nucleating agent, aheat-resistant stabilizer, an anti-weathering stabilizer, an antistaticagent, a coloring agent, a lubricant, a flame retardant, and ananti-blooming agent.

Crosslinking Agent

Examples of the crosslinking agent include sulfur, a sulfur compound andan organic peroxide.

Examples of the sulfur include powder sulfur, precipitated sulfur,colloidal sulfur, surface treatment sulfur, insoluble sulfur, etc.

Examples of the sulfur compound include sulfur chloride, sulfurdichloride, and high molecular polysulfide. Also, the sulfur compoundthat undergoes crosslinking by liberating activated sulfur atcrosslinking temperature, for example, morpholine disulfide, alkylphenoldisulfide, tetramethylthiuram disulfide, dipentamethylenethiuramtetrasulfide, selenium dimethyldithiocarbamate, etc. may also be used.In addition, in the case where the sulfur or the sulfur compound is usedas the crosslinking agent, it is preferable to use in combination withthe crosslinking promoter.

Specific examples of the organic peroxide include alkylperoxides such asdicumyl peroxide (DCP), di-t-butyl peroxide,di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide,di-t-amyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3,2,5-dimethyl-2,5-di(benzolyperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)-hexane,α,α′-bis(t-butylperoxy-m-isopropyl)benzene, and t-butylhydroperoxides;peroxyesters such as t-butylperoxy acetate, t-butylperoxy isobutyrate,t-butylperoxy pivalate, t-butylperoxy maleate, t-butylperoxyneodecanoate, t-butylperoxy benzoate, di-t-butylperoxy phthalate; andketone peroxides such as dicyclohexanone peroxide. The organic peroxidemay be used alone or in combination with two or more peroxides.

Among them, the organic peroxide that a one-minute half-life is in therange of from 130 to 200° C. is preferable; specifically dicumylperoxide, di-t-butyl peroxide,di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide,di-t-amyl peroxide, t-butyl hydroperoxide, and2,5-dimethyl-2,5-di-(t-butylperoxy)-hexane are preferable. Furthermore,in the case where the organic peroxide is used as the crosslinkingagent, it is preferable to use in combination with the crosslinkingauxiliary agent.

Among various kinds of the crosslinking agent, use of the sulfur or asulfur-based compound, particularly use of the sulfur is preferablesince a crosslinked product with excellent characteristics can beobtained. However, the organic peroxide is more preferable because ofexcellent degree of crosslinking.

In the case where the crosslinking agent is the sulfur or thesulfur-based compound, the corsslinking agent is usually used in therange of from 0.5 to 10 parts by weight, preferably from 0.5 to 9 partsby weight, and more preferably from 0.5 to 8 parts by weight withrespect to 100 parts by weight of the adhesive resin and the adhesiveresin composition.

In the case where the crosslinking agent is the organic peroxide, thecrosslinking agent is used in the range of from 0.05 to 3.0 parts byweight, preferably from 0.1 to 1.5 parts by weight with respect to 100parts by weight of the adhesive resin and the adhesive resincomposition.

In addition, the crosslinking agent is used usually in the range of from1×10⁻⁵ to 1×10⁻¹ mole, preferably from 1×10⁻⁵ to 1×10⁻² mole withrespect to 100 grams of the adhesive resin and the adhesive resincomposition described above.

Furthermore, whether the composition is crosslinked or not can be judgedby finding out whether or not, after boiling the composition of thepresent invention for more than 4 hours in boiling xylene, the amount ofresidue filtered using a wire gauze of 400 mesh is more than 10 parts byweight with respect to 100 parts by weight of the adhesive resin and theadhesive resin composition described above.

Filler

The filler has either strengthening properties or does not havestrengthening properties. The filler with strengthening propertiesenhances mechanical properties such as tensile strength, tear strength,and wear resistance. Specific examples of the filler with strengtheningproperties include a carbon black product such as SRF, GPF, FEF, MAF,HAF, ISAF, SAF, FT, and MT, a product derived by surface treatmentthereof with a silane coupling agent, silica, activated calciumcarbonate, and talc fine powder.

Crosslinking Promoter

Specific examples of the crosslinking promoter include thiazole-basedcompounds such as N-cyclohexyl-2-benzothiazole sulfenamide (CBZ),N-oxydiethylene-2-benzothiazole sulfenamide,N,N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole,2-(2,4-dinitrophenyl)mercaptobenzothiazole,2-(2,6-diethyl-4-morphorinothio)benzothiazole, and dibenzothiazylsulfide; guanidine compounds such as diphenylguanidine (DPG),triphenylguanidine, di-orthonitrileguanidine, orthonitrile biguanide,and diphenylguanidine phthalate; aldehyde-amine oraldehyde-ammonia-based compounds such as an acetaldehyde-anilinereaction product, butyraldehyde-aniline condensate,hexamethylenetetramine, and acetaldehyde-ammonia; imidazoline-basedcompound such as 2-mercaptoimidazoline; thiourea-based compounds such asthiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea,and di-orthotolylthiourea; thiuram-based compounds such astetramethylthiuram monosulfide; tetramethylthiuram disulfide,tetraethylthiuram disulfide, tetrabutylthiuram disulfide, andpentamethylenethiuram tetrasulfide; dithioate-based compounds such aszinc dimthyldithiocarbamate, zinc diethyldithiocarbamate, zincdi-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zincbutylphenyldithiocarbamate, sodium dimethyldithiocarbamate, seleniumdimethyldithiocarbamate, and tellurium dimethyldithiocarbamate;xanthate-based compounds such as zinc dibutylxanthate; and a compoundsuch as zinc white. The crosslinking promoters is used in the range offrom 1 to 20 parts by weight, preferably from 2 to 10 parts by weightwith respect to 100 parts by weight of the adhesive resin and theadhesive resin composition.

Crosslinking Auxiliary Agent

The crosslinking auxiliary agent is used in crosslinking with theorganic peroxide. Specific examples of the crosslinking auxiliary agentinclude sulfur; quinonedioxime-based compounds such as p-quinonedioximeand p,p′-dibenzoylquinonedioxime; and polyfunctional monomers, i.e.,(meth)acrylate-based compounds such as trimethylol propane triacrylateand polyethyleneglycol dimethacrylate; allylic compounds such asdiallylphthalate, triallylcyanurate; maleimide-based compounds such asN,N′-m-phenylenebismaleimide; and divinylbenzene. The crosslingkingauxiliary agent is used in the range of from 0.5 to 2 mole per 1 mole ofthe organic peroxide, and preferably by about the same amount as theorganic peroxide. If the amount of the crosslinking auxiliary agentexceeds the amount described above, the crosslinking reaction proceedsexcessively, which may reduce fluidity of the composition, lowermoldability, and increase the unreacted monomer component remaining inthe composition.

Softening Agent

Specific examples of the softening agent include petroleum-basedsoftening agents such as process oil, lubricating oil, paraffin, liquidparaffin, petroleum asphalt, and vaseline; coal tar-based softeningagents such as coal tar and coal tar pitch; fatty oil-based softeningagents such as castor oil, linseed oil, rapeseed oil, and coconut oil;tall oil; sub (or rubber substitute); waxes such as bees wax, carnaubawax, and lanolin; fatty acid and fatty acid salts such as ricinolicacid, palmitic acid, barium stearate, calcium stearate, and zinclaurate; and synthetic polymer substances such as petroleum resin,atactic polypropylene, and coumarone-indene resin. Among them, thepetroleum-based softening agent is preferably used, and particularly theprocess oil is preferably used. The softening agent is used in the rangeof 200 parts by weight or less, preferably in the range of from 5 to 200parts by weight, more preferably from 10 to 150 parts by weight, andparticularly preferably from 10 to 100 parts by weight with respect to100 parts by weight of the adhesive resin and the adhesive resincomposition.

Foaming Agent

Specific examples of the foaming agent include inorganic foaming agentssuch as sodium bicarbonate, sodium carbonate, ammonium bicarbonate,ammonium carbonate, and ammonium nitrite; nitroso compounds such asN,N′-dimethyl-N,N′-dinitrosoterephthalamide andN,N′-dinitrosopentamethylenetetramine; azo compounds such asazodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile,azoaminobenzene, and barium azodicarboxylate; sulfonyl hydrazidecompounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide,p,p′-oxybis(benzenesulfonyl hydrazide), and diphenylsulfone-3,3′-disulfonyl hydrazide; and azide compounds such as calciumazide, 4,4-diphenyl disulfonyl azide, and p-toluenesulfonyl azide. Amongthem, the nitroso compound, the azo compound and the azide compound arepreferable. The foaming agent is used in the range of from 0.5 to 30parts by weight, preferably from 1 to 20 parts by weight with respect to100 parts by weight of the adhesive resin and the adhesive resincomposition. From the adhesive resin and the adhesive resin compositioncontaining the foaming agent in the amount stated above, a foam with theapparent specific gravity in the range of from 0.03 to 0.8 g/cm³ can bemanufactured.

Foaming Auxiliary Agent

The foaming auxiliary agent can be used with the foaming agent.Concurrent use of the foaming auxiliary agent is effective in reducingdecomposition temperature of the foaming agent, acceleratingdecomposition, and homogenization of foams. Examples of the foamingauxiliary agent include organic acids such as salicylic acid, phthalicacid, stearic acid, and oxalic acid, urea or derivatives thereof. Thefoaming auxiliary agent is used in the range of from 0.01 to 10 parts byweight, and preferably from 0.1 to 5 parts by weight with respect to 100parts by weight of the adhesive resin and the adhesive resincomposition.

Processing Auxiliary Agent

The processing auxiliary agent that is generally added to rubbers can bewidely used. Specific examples of the processing auxiliary agent includea higher fatty acid such as ricinolic acid, stearic acid, palmitic acid,and lauric acid, and a salt of the higher fatty acid such as bariumstearate, zinc stearate, calcium stearate, or esters of the higher fattyacid.

The processing auxiliary agent is suitably used in the range of 10 partsby weight or less, and preferably in the range of 5 parts by weight orless per 100 parts by weight of the adhesive resin and the adhesiveresin composition.

Inorganic Filler

Specific examples of the inorganic filler include natural silicic acidsor silicates such as fine powder talc, kaolinite, sintered clay,pyrophyllite, sericite, and wallastonite; a carbonate such asprecipitated calcium carbonate, heavy calcium carbonate, and magnesiumcarbonate; a hydroxide such as aluminum hydroxide and magnesiumhydroxide; oxides such as zinc oxide, zinc white, and magnesium oxide;powder fillers of synthetic silicic acid or silicate such as hydrouscalcium silicate, hydrous aluminum silicate, hydrous silicic acid, andanhydrous silicic acid; flaky fillers such as mica; fibrous fillers suchas basic magnesium sulfate whisker, calcium titanate whisker, aluminumborate whisker, sepiolite, PMF (Processed Mineral Fiber), xonotlite,potassium titanate, and ellestadite; and balloon fillers such as glassballoon and fly ash balloon.

Among them, in the present invention, the talc is preferably used, andparticularly the fine powder talc with an average particle size in therange of from 0.01 to 10 μm is preferably used. Note that the averageparticle size of the talc can be measured by a liquid-phaseprecipitation method.

The inorganic filler used in the present invention, particularly thetalc may be unprocessed or pre-processed with surface treatment.Specific examples of the surface treatment include a chemical orphysical process using treatment agents such as silane coupling agent,higher fatty acid, metal salt of fatty acid, unsaturated organic acid,organic titanate, resin acid, and polyethylene glycol. Use of the talcthus surface treated can produce molded articles with excellent weldstrength, coatability, and moldability.

Two or more of the inorganic fillers described above may be concurrentlyused.

Also, in the present invention, together with the inorganic filler, theorganic filler such as high styrene (rubber), lignin, and reclaimedrubber can be also used.

Crystal Nucleating Agent

Various nucleating agents known as the crystal nucleating agents areused without any particular limitation. Aromatic phosphoric ester salt,benzylidenesorbitol, aromatic carboxylic acid, rosin-based nucleatingagents described below can be listed as examples of the crystalnucleating agent.

As the aromatic phosphoric ester salt, a compound represented by thefollowing formula (9) can be given.

-   -   (wherein R⁹ is an oxygen atom, a sulfur atom, or a hydrocarbon        group having from 1 to 10 carbon atoms, R¹⁰ and R¹¹ are a        hydrogen atom or a hydrocarbon group having from 1 to 10 carbon        atoms, and R¹⁰ and R¹¹ may be the same or different, or form a        ring structure comprising R¹⁰ bonded to R¹⁰, or R¹¹ bonded to        R¹¹ or R¹⁰ and R¹¹ bonded to each other and M is a metal atom        having from 1 to 3 valences, and n is an integer between 1        and 3. R¹⁰ may be all the same or different, and R¹¹ may be all        the same or different.)

Specific examples of the compound represented by the aforementionedformula (I) include the following compounds, and mixtures of two or morethereof: sodium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate,sodium-2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate,lithium-2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,sodium-2,2′-ethylidene-bis(4-1-propyl-6-t-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4-methyl-6-t-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4-ethyl-6-t-butylphenyl)phosphate,calcium-bis[2,2′-thiobis(4-methyl-6-t-butylphenyl)phosphate],calcium-bis[2,2′-thiobis(4-ethyl-6-t-butylphenyl)phosphate],calcium-bis[2,2′-thiobis-(4,6-di-t-butylphenyl)phosphate],magnesium-bis-[2,2′-thiobis(4,6-di-t-butylphenyl)phosphate],magnesium-bis[2,2′-thiobis-(4-t-octylphenyl)phosphate],sodium-2,2′-butylidene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-butylidene-bis(4,6-di-t-butylphenyl)phosphate,sodium-2,2′-t-octylmethylene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-t-octylmethylene-bis(4,6-di-t-butylphenyl)phosphate,calcium-bis-(2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate),magnesium-bis[2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate],barium-bis[2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate],sodium-2,2′-methylene-bis(4-methyl-6-t-butylphenyl)phosphate,sodium-2,2′-methylene-bis(4-ethyl-6-t-butylphenyl)phosphate,sodium(4,4′-dimethyl-5,6′-di-t-butyl-2,2′-biphenyl)phosphate,calcium-bis[(4,4′-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl)phosphate],sodium-2,2′-ethylidene-bis(4-m-butyl-6-t-butylphenyl)phosphate,sodium-2,2′-methylene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-methylene-bis(4,6-di-ethylphenyl)phosphate,potassium-2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,calcium-bis[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate],magnesium-bis[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate],barium-bis[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate],aluminum-tris[2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate, andaluminum-tris[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate. Inparticular, sodium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate ispreferable.

As the aromatic phosphoric ester salt, a compound represented by thefollowing formula (10) can be given.

-   -   (wherein each R¹² may be the same or different, and is a        hydrogen atom or a hydrocarbon group having from 1 to 10 carbon        atoms, M is a metal atom having from 1 to 3 valences, and n is        an integer between 1 and 3.)

Specific examples of the compound represented by the aforementionedformula (11) include the following compounds, and mixtures of two ormore thereof: sodium-bis(4-t-butylphenyl)phosphate,sodium-bis(4-methylphenyl)phosphate, sodium-bis(4-ethylphenyl)phosphate,sodium-bis(4-1-propylphenyl)phosphate,sodium-bis(4-t-octylphenyl)phosphate,potassium-bis(4-t-butylphenyl)phosphate,calcium-bis(4-t-butylphenyl)phosphate,magnesium-bis(4-t-butylphenyl)phosphate,lithium-bis(4-t-butylphenyl)phosphate, andaluminum-bis(4-t-butylphenyl)phosphate. In particular,sodium-bis(4-t-butylphenyl)phosphate is preferable.

As the benzylidenesorbitol, a compound represented by the followingformula (11) can be given.

-   -   (wherein each R¹³ may be the same or different, and is a        hydrogen atom or a hydrocarbon group having from 1 to 10 carbon        atoms, and m and n are integers from 0 to 5, respectively.)

Specific examples of the compound represented by the aforementionedformula (111) include the following compounds, and mixtures of two ormore thereof: 1,3,2,4-dibenzylidenesorbitol,1,3-benzylidene-2,4-p-methylbenzylidenesorbitol,1,3-benzylidene-2,4-p-ethylbenzylidenesorbitol,1,3-p-methylbenzylidene-2,4-benzylidenesorbitol,1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol,1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol,1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol,1,3,2,4-di(p-methylbenzylidene)sorbitol,1,3,2,4-di(p-ethylbenzylidene)sorbitol,1,3,2,4-di(p-n-propylbenzylidene)sorbitol,1,3,2,4-di(p-1-propylbenzylidene)sorbitol,1,3,2,4-di(p-n-butylbenzylidene)sorbitol,1,3,2,4-di(p-s-butylbenzylidene)sorbitol,1,3,2,4-di(p-t-butylbenzylidene)sorbitol,1,3,2,4-di(2′,4′-dimethylbenzylidene)sorbitol,1,3,2,4-di(p-methoxybenzylidene)sorbitol,1,3,2,4-di(p-ethoxybenzylidene)sorbitol,1,3-benzylidene-2,4-p-chlorobenzylidenesorbitol,1,3-p-chlrorobenzylidene-2,4-benzylidenesorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol,1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol,1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol,1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol, and1,3,2,4-di-(p-chlorobenzylidene)sorbitol. In particular,1,3,2,4-dibenzylidenesorbitol, 1,3,2,4-di(p-methylbenzylidene)sorbitol,1,3,2,4-di(p-ethylbenzylidene)sorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol,1,3,2,4-di(p-chlorobenzylidene)sorbitol, and mixtures of two or more ofthese compounds are preferable.

Among the benzylidenesorbitol described above, a compound represented bythe following formula (12) is given as a prefered example.

-   -   (wherein each R¹⁴ may be the same or different, and is a methyl        group or an ethyl group.)

As the aromatic carboxylic acid, aluminum hydroxy-di-p-t-butylbenzoaterepresented by the following formula (13) is given.

The rosin-based crystal nucleating agent is, for example, metal salt ofrosin acid, and the metal salt of the rosin acid refers to a reactionproduct between the rosin acid and a metal compound. Examples of therosin acid include natural rosin such as gum rosin, tall oil rosin, andwood rosin; various kinds of a modified rosin such as disproportionatedrosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, andα,β-ethylenically unsaturated carboxylic acid-modified rosin; a purifiedproduct of the aforementioned natural rosin, and a purified product ofthe aforementioned modified rosin. In addition, examples of theunsaturated carboxylic acid used for preparation of the aforementionedα,β-ethylenically unsaturated carboxylic acid-modified rosin includemaleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconicanhydride, citraconic acid, acrylic acid, and methacrylic acid. Amongthem, at least one rosin acid selected from a group comprising thenatural rosin, modified rosin, purified product of the natural rosin,and purified product of the modified rosin is preferable. In the above,examples of the rosin acid include plural resin acids selected frompimaric acid, sandaracopimaric acid, parastric acid, isopimaric acid,abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid,dihydroabietic acid, and tetrahydroabietic acid.

The metal compound that forms metal salt in the reaction with theaforementioned rosin acid is a compound containing a metal element suchas sodium, potassium, and magnesium, and undergoing salt formation withthe aforementioned rosin acid. Specific examples thereof includechloride, nitrate, acetate, sulfate, carbonate, oxide, and hydroxide ofthe metal described above.

Other examples of the crystal nucleating agent include a highmelting-point polymer, a metal salt of an aromatic carboxylic acid andan aliphatic carboxylic acid, an inorganic compound, etc.

Examples of the high-melting point polymer include a polyvinylcycloalkane such as poly(vinylcyclohexane) and poly(vinylcyclopentane),poly(3-methyl-1-pentene), poly(3-methyl-1-butne), and a polyalkenylsilane.

Examples of the metal salt of the aromatic carboxylic acid and thealiphatic carboxylic acid include aluminum benzoate, aluminump-t-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, andsodium pyrrolecarboxylate.

(LC Polymer)

The LC polymer that is preferably used as an adherend for the adhesiveresin and the adhesive resin composition of the present invention is anaromatic polyester and/or an aromatic polyester-amide, generally calleda thermotropic LC polymer.

Specific examples thereof include (1) a polymer of a combination of anaromatic dicarboxylic acid, an aromatic diol and an aromatichydroxycarboxylic acid; (2) a polymer of a combination of differentkinds of aromatic hydroxycarboxylic acids; (3) polymer of a combinationof an aromatic dicarboxylic acid and a nuclear-substituted aromaticdiol, and (4) a polymer obtained by reacting a polyester such aspolyethylene terephthalate with an aromatic hydroxycarboxylic acid, andthe polymer forms an anisotropic melt at a temperature of not more than400° C. In addition, in place of the aromatic dicarboxylic acid,aromatic diol and aromatic hydroxycarboxylic acid, an ester-formingderivative thereof may also be used.

In the present invention, among examples of the LC polymer, the LCpolymer containing a monomer unit derived from one or more kinds,usually at least two kinds of monomers described below is preferablyused: terephthalic acid, isophthalic acid, 1,4-hydroquinone, resorcinol,4-aminobenzoic acid, 4-hydroxybenzoic acid, 4-aminophenol,1,4-phenylenediamine, 4,4′-biphenol, 4,4′-biphenyldicarboxylic acid,6-hydroxy-2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, and2,6-dihydroxynaphthalene.

(Molding Method)

A method of molding a laminated body comprising layers of the LC polymerusing the adhesive resin and the adhesive resin composition of thepresent invention is publicly known, including, for example, lamination,co-extrusion, extrusion lamination, and co-extrusion coating.

In this case, a preferable structure of the laminated body is formedwherein the layer containing the polyolefin and the layer containing theLC polymer are adhered with a layer comprising the adhesive resin andthe adhesive resin composition of the present invention.

The polyolefin used herein may be any of the aforementioned polyolefin.

Provided that these three layers are included, other layers may beincluded, and in an example of a five-layer structure, it may contain afirst layer of the polyolefin, a second layer comprising the adhesiveresin composition of the present invention, a third layer of the LCpolymer, a fourth layer comprising the adhesive resin of the presentinvention, and a fifth layer of the polyolefin.

In the following, the present invention will be described by way ofExamples, wherein it is to be noted that the present invention shouldnot be restricted to these Examples.

Method of Measurement of Physical Properties Used in the PresentInvention

(1) Density

A strand obtained during measurement of the melt flow rate at 190° C.under a load of 2.16 kg is subjected to heat treatment at 120° C. for 1hour, and is slowly cooled to room temperature over 1 hour, andsubsequently the density is measured using a density gradient tube.

(2) Melt Flow Rate (MFR)

MFR is measured under the load of 2.16 kg according to ASTM D1238-65T.

(3) Weight Average Molecular Weight (Mw) and Molecular WeightDistribution (Mw/Mn)

They were measured in the following manner using GPC-150C produced byMillipore Co., Ltd.

A separatory column of TSK GNH HT having a diameter of 72 mm and alength of 600 mm was used. The column temperature was set to 140° C. Asample (concentration: 0.1% by weight, amount: 500 μl) was moved in thecolumn at a rate of 1.0 ml/min using o-dichlorobenzene (Wako PureChemical Industries, Ltd.) as a mobile phase and 0.025% by weight of BHT(available from Takeda Chemical Industries, Ltd.) as an antioxidant. Adifferential refractometer was used as a detector. Standard polystyrenesavailable from Tosoh Corporation were used as those of Mw<1,000 andMw>4×10⁶, and standard polystyrenes available from Pressure Chemical Co.were used as those of 1,000<Mw<4×10⁶.

(4) Crystallinity

The crystallinity was determined by subjecting a pressed sheet having athickness of 1.0 mm to X-ray diffractometry after at least 24 hours hadpassed since the sheet was formed.

EXAMPLE 1

Using toluene as a reaction solvent, 50 g of ethylene/4-methyl-1-pentenecopolymer (LLDPE-1, density: 0.920 g/cc, the ethylene content: 97 mole%, MFR (at 190° C.): 20.0 g/10 minutes, and crystallinity: 49.6%) in 170ml of toluene was placed in a one-liter autoclave, and was dissolved at140° C. under a nitrogen atmosphere. Next, to this polymer solution, amixture of 5 g of glycidyl methacrylate and 5 g of styrene, and atoluene (40 ml) solution of dicumyl peroxide (1 g), each preparedbeforehand, were added by dropping from separate inlet tubes over 4hours. After the end of dropping, the reaction system was kept at thesame temperature for additional 2 hours. After ending the reaction, thesystem was cooled to room temperature, then the resultant polymersolution in toluene was injected into 3 liters of acetone, and left forpolymer precipitation. The precipitated polymer was filtered andrepeatedly washed with acetone, subsequently was dried overnight underreduced pressure at 80° C., and the desired modified ethylenic copolymerwas obtained.

Based on the elemental analysis and NMR spectroscopy of the preparedmodified ethylenic copolymer, the grafted amount of glycidylmethacrylate was found to be 1.0% by weight and the grafted amount ofstyrene to be 1.3% by weight. A film was prepared from the producedmodified ethylenic copolymer as described below, and the adhesivestrength to the LC polymer was measured in the following manner.

The results are shown in Table 1.

[Preparation of Films]

On a press plate an aluminum sheet of 0.1 mm in thickness, a polyimidesheet, and an aluminum sheet of 100 μm in thickness whose center portionwas cut out in a square of 20 cm×20 cm and removed were placed in thisorder, and in the center (where a portion of the sheet was cut out andremoved) 4.0 g of the sample (the modified polymer) was placed. Next,this was covered with a polyimide sheet, an aluminum sheet and a pressplate in this order.

The sample placed between the above press plates was put in a hot pressat 190° C., preheated for about 5 min, and pressurizing (at 50 kg/cm²-G)and depressurizing were repeated several times to remove bubbles in thesample. Next, the pressure was increased to 100 kg/cm²-G andpress-heated for 5 min. After depressurizing, the press plates wereremoved from the press and were then placed in a different press whosepressing surfaces were kept at 20° C., press-cooled at 100 kg/cm²-G for5 min, then depressurized, and the sample was taken out. A part of theso-prepared film (an adhesive resin sheet) whose thickness was found tobe uniform from about 150 to 170 μm was used for measurement of theadhesive strength.

Except for the change of press temperature, a press sheet of the LCpolymer (marketed product Vectran V300P, press temperature: 230° C.),and a press sheet of a high-density polyethylene (marketed product Hizex7000F, press temperature: 190° C.) were prepared.

[Measurement of the Adhesive Strength to the LC Polymer]

The press sheets prepared as above were superposed in the order of thehigh-density polyethylene/the adhesive resin composition/the LC polymer,and a laminated body comprising three layers was prepared at the presstemperature of 260° C., according to a procedure similar to [Preparationof films] described above. The laminated body thus obtained was cut inthe form of long strips of 15 mm in width, and the tear strength wasmeasured by tearing apart the adhesive interface between the LC polymerand the adhesive resin composition in the direction of 180° with a tearvelocity of 300 mm/min.

The measurement of the adhesive strength after immersion in gasoline wasperformed in the following way.

The laminated body comprising the high-density polyethylene/the adhesiveresin composition/the LC polymer was prepared according to a proceduresimilar to that used in the measurement of the adhesive strength asdescribed above. The laminated body thus obtained was cut in the form oflong strips of 15 mm in width, and was then immersed in standardgasoline (toluene/isooctane=50/50 mixture solution) at 40° C. for oneweek. After the end of immersion, a specimen taken out of the immersionbath was left for one day for conditioning of the state. Then the tearstrength was measured according to the procedure similar to thosedescribed above.

EXAMPLES 2 TO 10, COMPARATIVE EXAMPLE 1 AND 2

Tests were carried out similarly to that of EXAMPLE 1 except that thetest conditions were modified as described in Table 1. The results areshown in Table 1. TABLE 1 Example 1 Example 2 Example 3 Example 4Polyolefin LLDPE-1

LLDPE-2 (g) 50 50 50 50 Epoxy group GMA

containing  5 12.5 25  5 ethylenically unsaturated monomer (g) Aromaticvinyl St

monomer  5 12.5 25  5 (g) Radical DCP

initiator  1  1  1  1 (g) Grafted amount GMA/St

GMA/St (wt %) 1.0/1.3 2.4/2.3 4.0/4.2 1.0/1.3 Polymer adhesiveness toliquid crystal polymer (Kgf/15 mm) Initial adhesive  2.6  3.4 Base  2.6force material fractured After immersion  2.3  3.1 Base  2.0 in gasolinematerial fractured Comparative Comparative Example 5 Example 1 Example 2Polyolefin EBR-l LLDPE-1 EGMA (g) 50 50 Epoxy group GMA — — containing 5 ethylenically unsaturated monomer (g) Aromatic vinyl St — — monomer 5 (g) Radical initiator DCP — — (g)  1 Grafted amount GMA/St — — (wt %)1.1/1.4 Polymer adhesiveness to liquid crystal polymer (Kgf/15 mm)Initial adhesive  3.1 0.1 or less Base force material fractured Afterimmersion  0.5 0.1 or less 1.0 in gasoline Example Example 6 Example 7Example 8 Example 9 10 Polyolefin LLDPE-l

LLDPE-2 (g) 50 50 50 50 50 Epoxy 3, 4-

3, 4- 3, 4- group epoxy- 10 50 epoxy- epoxy- containing cyclo- cyclo-cyclo- ethylenically hexyl- hexyl- hexyl- unsaturated methyl- methyl-methyl- monomer acrylate acrylate acrylate (g) (ERA)  5  5  5 Aromatic —— St — — vinyl 50 monomer (g) Radical DCP

initiator  0.25  0.25  2  0.25  0.25 (g) Grafted  1.14  2.06 ERA/St 0.20  1.10 amount 3.1/3.5 (wt %) Polymer adhesiveness to liquid crystalpolymer (Kgf/15 mm) Initial  2.5  3.3 Base  2.3  2.5 adhesive materialforce fractured After  2.1  3.0 Base  2.0  2.2 immersion in materialgasoline fractured

Further, symbols and abbreviated notations of Table 1 are explainedbelow.

-   -   DCP: dicumyl peroxide    -   LLDPE-1: ethylene/4-methyl-1-pentene copolymer (density: 0.920        g/cc, ethylene content: 97 mole %, MFR (190° C.): 20 g/10        minutes, and crystallinity: 49.6%)    -   LLDPE-2: ethylene/hexene copolymer (density: 0.905 g/cc,        ethylene content: 95 mole %, MFR (190° C.): 20 g/10 minutes, and        crystallinity: 35%)    -   EBR-1: ethylene/1-butene copolymer (density: 0.888 g/cc,        ethylene content: 88 mole %, MFR (190° C.): 20 g/10 minutes, and        crystallinity: 12%)    -   GMA: glycidyl methacrylate    -   St: styrene    -   EBR-1: ethylene/1-butene copolymer (density: 0.888 g/cc,        ethylene content: 88 mole %, MFR (190° C.): 20 g/10 minutes, and        crystallinity: 12%)    -   EGMA: ethylene/glycidyl methacrylate copolymer (ethylene        content: 88 wt %)    -   [-] indicates “unused”, and [←] indicates “the same compounds to        the left was used”.

INDUSTRIAL APPLICABILITY

The adhesive resin and the adhesive resin composition of the presentinvention have an excellent adhesiveness to the liquid crystal polymerand excellent solvent resistance.

The adhesive resin and the adhesive resin composition of the presentinvention are applicable as products of any shape if used as adhesiveresins for multilayer structures including the liquid crystal polymerdescribed above, and in particular used preferably as adhesive resinsfor multilayer films, multilayer sheet, multilayer blow molded articles,and multilayer injection molded articles wherein the polyolefin and theliquid crystal polymer are laminated.

These multilayer structures can be used as packaging materials for foodpackaging and pharmaceuticals packaging, and as containers such asautomobile fuel tanks.

1. An adhesive resin for a liquid crystal polymer, comprising a modifiedpolyolefin (D) prepared by graft polymerizing at least one epoxygroup-containing ethylenically unsaturated monomer (B) to a polyolefin(A) obtained by polymerizing one or more olefins selected from ethyleneand α-olefin having from 3 to 20 carbon atoms, in an amount in the rangeof from 0.01 to 50% by weight, with the proviso that the modifiedpolyolefin is 100% by weight.
 2. The adhesive resin for the liquidcrystal polymer according to claim 1, wherein the modified polyolefin(D) is a modified polyolefin (D-1) formed by graft polymerizing 0.01 to20% by weight of the epoxy group-containing ethylenically unsaturatedmonomer (B) to the polyolefin (A) wherein the polyolefin (A) is anethylene homopolymer (A-1) or a copolymer (A-2) of ethylene and at leastone α-olefin selected from α-olefin having from 3 to 20 carbon atoms,the ethylene homopolymer (A-1) or the copolymer (A-2) having a densityof 0.895 g/cc or more, and a melt flow rate (190° C. and a load of 2.16kg) within the range of from 0.01 to 500 g/10 minutes.
 3. The adhesiveresin for the liquid crystal polymer according to claim 1, wherein themodified polyolefin (D) is a modified polyolefin (d-1) formed by graftpolymerizing 0.01 to 20% by weight of the epoxy group-containingethylenically unsaturated monomer (B) and 0.01 to 20% by weight of anaromatic vinyl monomer (C) to the polyolefin (A) wherein the polyolefin(A) is an ethylene homopolymer (A-1) or a copolymer (A-2) of ethyleneand at least one α-olefin selected from α-olefin having from 3 to 20carbon atoms, the ethylene homopolymer (A-1) or the copolymer (A-2)having a density of 0.895 g/cc or more and a melt flow rate (190° C. anda load of 2.16 kg) within the range of from 0.01 to 500 g/10 minutes. 4.The adhesive resin for the liquid crystal polymer according to claim 3,wherein the mole ratio of the grafted amount represented by (the epoxygroup-containing ethylenically unsaturated monomer (B)): (the aromaticvinyl monomer (C)) in the modified polyolefin (d-1) is in the range offrom 10:90 to 95:5.
 5. The adhesive resin for the liquid crystal polymeraccording to claim 1, wherein the modified polyolefin (D) is a modifiedpolyolefin (D-2) prepared by graft polymerizing at least one alicyclicepoxy group-containing ethylenically unsaturated monomer represented bythe following formulae (1) to (5) to a polyolefin (A) obtained bypolymerizing one or more olefins selected from ethylene and α-olefinhaving from 3 to 20 carbon atoms, in an amount in the range of from 0.01to 50% by weight, with the proviso that the modified polyolefin (D) is100% by weight:

(wherein R₁ is a hydrogen atom or a methyl group, R₂ is a single bond ora bivalent hydrocarbon group having from 1 to 20 carbon atoms andoptionally containing hetero atoms, R₃ is a hydrogen atom or ahydrocarbon group having from 1 to 20 carbon atoms and optionallycontaining hetero atoms, and n is an integer of 0 to 2, with the provisothat R₃ may be all the same or different from each other).
 6. Theadhesive resin for the liquid crystal polymer according to claim 5,wherein the resin comprises the modified polyolefin (D-2) prepared bygraft polymerizing at least one alicyclic epoxy group-containingethylenically unsaturated monomer (B) represented by the above formulae(1) to (5) in the range of from 0.01 to 50% by weight, and the otherethylenically unsaturated monomer in the range of from 0.01 to 50% byweight to a polyolefin (A) obtained by polymerizing one or more olefinsselected from ethylene and α-olefin having from 3 to 20 carbon atoms,with the proviso that the modified polyolefin is 100% by weight and thetotal grafted amount of (B) and the other ethylenically unsaturatedmonomer is in the range of from 0.02 to 60% by weight.
 7. The adhesiveresin for the liquid crystal polymer according to claim 5, wherein thepolyolefin (A) is an ethylene homopolymer or an ethylenic copolymer. 8.The adhesive resin for the liquid crystal polymer according to claim 5,wherein the polyolefin (A) is the ethylene homopolymer or the ethyleniccopolymer having a density of 0.895 g/cc or more.
 9. The adhesive resinfor the liquid crystal polymer according to claim 6, wherein the otherethylenically unsaturated monomer is the aromatic vinyl monomer.
 10. Anadhesive resin composition for the liquid crystal polymer, comprisingthe modified polyolefin (D) according to claim 1 and a thermoplasticresin (E).
 11. The adhesive resin composition for the liquid crystalpolymer according to claim 10, wherein the thermoplastic resin (E) isthe polyolefin.
 12. The adhesive resin composition for the liquidcrystal polymer according to claim 10, wherein the thermoplastic resin(E) is at least one ethylenic polymer selected from a group consistingof an ethylene homopolymer and a copolymer of ethylene and at least oneα-olefin having from 3 to 20 carbon atoms.
 13. The adhesive resincomposition for the liquid crystal polymer according to claim 10,wherein the modified polyolefin (D) is contained in the range of from 1to 90% by weight.